EP2101368B1 - Separator for non-aqueous rechargeable lithium battery - Google Patents
Separator for non-aqueous rechargeable lithium battery Download PDFInfo
- Publication number
- EP2101368B1 EP2101368B1 EP08253971.9A EP08253971A EP2101368B1 EP 2101368 B1 EP2101368 B1 EP 2101368B1 EP 08253971 A EP08253971 A EP 08253971A EP 2101368 B1 EP2101368 B1 EP 2101368B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- separator
- separator body
- composite
- separator according
- buffer layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229910052744 lithium Inorganic materials 0.000 title claims description 33
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims description 32
- 239000002131 composite material Substances 0.000 claims description 35
- -1 polypropylene Polymers 0.000 claims description 30
- 150000002484 inorganic compounds Chemical class 0.000 claims description 28
- 229910010272 inorganic material Inorganic materials 0.000 claims description 28
- 150000002894 organic compounds Chemical class 0.000 claims description 28
- 238000002844 melting Methods 0.000 claims description 17
- 230000008018 melting Effects 0.000 claims description 17
- 239000004698 Polyethylene Substances 0.000 claims description 15
- 229920000573 polyethylene Polymers 0.000 claims description 15
- 239000011148 porous material Substances 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 9
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 8
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 8
- 239000004760 aramid Substances 0.000 claims description 8
- 229920003235 aromatic polyamide Polymers 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 229910052593 corundum Inorganic materials 0.000 claims description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 5
- 229910007822 Li2ZrO3 Inorganic materials 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- 229910010177 Li2MoO3 Inorganic materials 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- ZFTFAPZRGNKQPU-UHFFFAOYSA-N dicarbonic acid Chemical compound OC(=O)OC(O)=O ZFTFAPZRGNKQPU-UHFFFAOYSA-N 0.000 claims description 3
- XRASRVJYOMVDNP-UHFFFAOYSA-N 4-(7-azabicyclo[4.1.0]hepta-1,3,5-triene-7-carbonyl)benzamide Chemical compound C1=CC(C(=O)N)=CC=C1C(=O)N1C2=CC=CC=C21 XRASRVJYOMVDNP-UHFFFAOYSA-N 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 239000004745 nonwoven fabric Substances 0.000 claims description 2
- 230000000052 comparative effect Effects 0.000 description 13
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 9
- 230000006866 deterioration Effects 0.000 description 9
- 239000008151 electrolyte solution Substances 0.000 description 9
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 8
- 229910001429 cobalt ion Inorganic materials 0.000 description 8
- 230000014759 maintenance of location Effects 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 230000007704 transition Effects 0.000 description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- 239000011149 active material Substances 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 229910032387 LiCoO2 Inorganic materials 0.000 description 4
- 230000008602 contraction Effects 0.000 description 4
- 239000011267 electrode slurry Substances 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000011255 nonaqueous electrolyte Substances 0.000 description 4
- 239000003495 polar organic solvent Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- 239000006258 conductive agent Substances 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- 229910000686 lithium vanadium oxide Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- RLTFLELMPUMVEH-UHFFFAOYSA-N [Li+].[O--].[O--].[O--].[V+5] Chemical compound [Li+].[O--].[O--].[O--].[V+5] RLTFLELMPUMVEH-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910003480 inorganic solid Inorganic materials 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000005518 polymer electrolyte Substances 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910007966 Li-Co Inorganic materials 0.000 description 1
- 229910013454 LiC4 Inorganic materials 0.000 description 1
- 229910013458 LiC6 Inorganic materials 0.000 description 1
- 229910000552 LiCF3SO3 Inorganic materials 0.000 description 1
- 229910008295 Li—Co Inorganic materials 0.000 description 1
- 229910026161 MgAl2O4 Inorganic materials 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical class C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002388 carbon-based active material Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229920000547 conjugated polymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- KLKFAASOGCDTDT-UHFFFAOYSA-N ethoxymethoxyethane Chemical compound CCOCOCC KLKFAASOGCDTDT-UHFFFAOYSA-N 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 125000000457 gamma-lactone group Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 229910001547 lithium hexafluoroantimonate(V) Inorganic materials 0.000 description 1
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910001537 lithium tetrachloroaluminate Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 229940058401 polytetrafluoroethylene Drugs 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- OEBIHOVSAMBXIB-SJKOYZFVSA-N selitrectinib Chemical compound C[C@@H]1CCC2=NC=C(F)C=C2[C@H]2CCCN2C2=NC3=C(C=NN3C=C2)C(=O)N1 OEBIHOVSAMBXIB-SJKOYZFVSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/417—Polyolefins
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/423—Polyamide resins
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/431—Inorganic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
- H01M50/457—Separators, membranes or diaphragms characterised by the material having a layered structure comprising three or more layers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/463—Separators, membranes or diaphragms characterised by their shape
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/491—Porosity
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- a buffer layer of a composite including the organic compound and the inorganic compound is formed, so that the separator body is supported by the composite.
- the positive electrode and negative electrode are obtained by mixing the active material with an additive(s) suitably selected from the group consisting of a conductive agent, a binder, a filler, a dispersing agent, an ion conductive agent, and a pressure enhancer.
- an additive(s) suitably selected from the group consisting of a conductive agent, a binder, a filler, a dispersing agent, an ion conductive agent, and a pressure enhancer.
- Suitable solvents for a non-aqueous electrolyte include cyclic esters such as ethylene carbonate, propylene carbonate, and so on; linear esters such as dimethyl carbonate, diethyl carbonate, methylethyl carbonate, and so on; ⁇ - lactones such as ⁇ -butyl lactone; linear ethers such as 1,2-dimethoxy ethane, 1,2-diethoxy ethane, ethoxymethoxy ethane, and so on; cyclic ethers such as tetrahydrofurans; and nitriles such as acetonitrile and so on.
- cyclic esters such as ethylene carbonate, propylene carbonate, and so on
- linear esters such as dimethyl carbonate, diethyl carbonate, methylethyl carbonate, and so on
- ⁇ - lactones such as ⁇ -butyl lactone
- linear ethers such as 1,2-dimethoxy
- Each of non-aqueous rechargeable lithium cells prepared according to Examples 1 to 9 and comparative example was charged at a constant current of 0.5C and constant voltage of 4.3V, and were then discharged to a discharge end voltage of 2.75V at 0.5C, and repeated for 200 cycles.
- the capacity retention ratio was measured after completing the 200 cycles and the results are provided in Table 1. Examples marked with a "*" are included by way of reference.
Description
- The present invention relates to a separator for a non-aqueous rechargeable lithium battery.
- Conventional non-aqueous rechargeable lithium batteries have a separator including an electrically insulating porous film between a positive electrode and a negative electrode, and an electrolyte solution in which dissolved lithium salt is impregnated in the film pores. Such a non-aqueous rechargeable lithium battery has excellent characteristics such as high capacity and high energy density.
- The positive electrode or the negative electrode of conventional non-aqueous rechargeable lithium batteries has an active material of a transition metal compound. For example, when the positive active material includes a Li-Co-based oxide, such as LiCoO2, trivalent cobalt ions (Co3+) are converted to unstable quadrivalent cobalt ions (Co4+) by the intercalation reactions of lithium ions during the charge and discharge cycles. The quadrivalent cobalt ions then react with an electrolyte solution to oxidize the electrolyte solution and are reduced to divalent cobalt ion (Co2+). The divalent cobalt ions tend to dissolve in the electrolyte solution, and move to the negative electrode, where they are reduced and precipitated as cobalt metal. When the cobalt metal is deposited and accumulated in the negative electrode, the separator and/or the negative electrode may get damaged and the charge and discharge characteristics of the non-aqueous rechargeable lithium battery may also deteriorate accordingly.
- In addition, when the quadrivalent cobalt ions are reduced to divalent cobalt ions, the separator may also oxidize and deteriorate. For example, when a separator is composed of polyethylene, the hydrogen atoms are removed by the oxidation reaction, leaving behind only carbons as backbones in the polyethylene molecules. Such a carbonated separator can easily be damaged because of its weak mechanical strength.
- As mentioned above, conventional non-aqueous rechargeable lithium batteries have charge and discharge problems because the electrolyte solution decomposition material is deposited on the negative electrode (or positive electrode), and because of the oxidized separator.
- Furthermore, due to the high capacity and high energy density in the conventional rechargeable battery, short circuits could occur both inside and outside of the battery, and the battery temperature could rapidly increase. For these reasons, conventional separators typically include a porous film of polyethylene having a melting point ranging from 120 to 140° C. These separators have excellent shutdown characteristic and handling property, and are low in cost.
- The shutdown characteristic refers to the core being closed and the current being blocked due to a battery temperature increase from an overcharge or an inside or outside short, so a part of the separator is fused. In other words, as the battery temperature increases, the separator fuses and rapidly contracts, or gets damaged, so the short circuit occurs.
- Therefore, in order to improve the safety of the non-aqueous rechargeable lithium battery, it has been attempted to improve the heat resistance of the electrode materials, particularly the separators. Various attempts to improve or ensure battery safety even when the separator is rapidly contracted or damaged have been tried.
- Other attempts to improve or ensure battery safety include providing a rechargeable battery mounted with a separator including a heat-resisting nitrogen aromatic polymer and a ceramic powder; a rechargeable battery mounted with a porous film composed of an inorganic oxide filler and a film binder on the surface of a positive electrode or a negative electrode; and a rechargeable battery mounted with a separator including a mixture of a filler having a melting point of 250° C or more and a filler having a melting point ranging from 80 to 120° C.
- However, in such rechargeable batteries, the deterioration of a rechargeable battery due to the transition metal included in the electrode has never been considered.
-
WO2007/049568 ,WO2006/068428 ,EP2169743 (cited under Article 54(3) EPC),US2007281206 ,WO2006061936 ,EP1146576 andUS4650730 disclose separators that contain inorganic particles. - An embodiment of the present invention provides a separator for a non-aqueous rechargeable lithium battery. Another embodiment of the present invention provides a separator for a non-aqueous rechargeable lithium battery that is less prone to deterioration, prevents or reduces short circuits from occurring, and prevents or reduces the deterioration of an electrode by stabilizing the transition elements in the electrode.
- A further embodiment of the present invention provides a non-aqueous rechargeable lithium battery including the separator.
- The embodiments of the present invention are not limited to the above technical purposes, and a person of ordinary skill in the art can understand other technical purposes.
- According to one embodiment of the present invention, a separator for a non-aqueous rechargeable lithium battery is provided. The separator includes a separator body and a composite including an organic compound and an inorganic compound supporting the separator body. The organic compound has a higher melting point than that of the material composing the separator body, and the inorganic compound is selected from the group consisting of Al2(SO4)3, Al2(SO4)3·Al(OC2H5)3 Li2MoO3 Al2O3·AlPO4, Li2ZrO3, and combinations thereof.
- On the surface of the separator body facing the positive electrode and/or the surface facing to the negative electrode, a buffer layer of a composite including the organic compound and the inorganic compound is formed, so that the separator body is supported by the composite.
- The separator body is supported by the composite because the composite, which contains the organic compound and inorganic compound, fills the pores of the separator body.
- In addition, the buffer layer(s) of the composite including the organic compound and the inorganic compound is formed on the surface of the separator body facing the positive electrode and/or the surface facing the negative electrode, and the composite including the organic compound and inorganic compound fills the pores of the separator body, so that the separator body is supported by the composite.
- According to another embodiment of the present invention, a non-aqueous rechargeable lithium battery is provided. The non-aqueous rechargeable lithium battery includes a separator including a separator body and a composite including an organic compound and an inorganic compound supporting the separator body; a positive electrode facing one surface of the separator body; and a negative electrode facing to the other opposite surface. The organic compound has a higher melting point than that of a material of the separator body. The inorganic compound is selected from the group consisting of Al2(SO4)3, Al2(SO4)3·Al(OC2H5)3 Li2MoO3, Al2O3·AlPO4, Li2ZrO3, and combinations thereof.
- According to a first aspect of the invention, there is provided a separator as set out in
claim 1. Preferred features of this aspect are set out in claims 2 to 12. - According to a second aspect of the invention, there is provided a non-aqueous rechargeable lithium battery as set out in claim 13.
- Further embodiments of the present invention will also be described in detail.
- In the separator for the non-aqueous rechargeable lithium battery according to the present invention, it is possible to provide a separator that is less prone to rapid contractions and damage, and accordingly, it is possible to provide a non-aqueous rechargeable lithium battery having an electrode or a separator that is less prone to deterioration after repeated charge and discharge.
-
-
FIG. 1A is a graph showing an FT-IR analysis result of the separator prepared according to Example 2. -
FIG. 1B is a graph showing an FT-IR analysis result of the separator prepared according to a Comparative Example. -
FIG. 2 is a cross-sectional view of a battery according to on one embodiment of the present invention. - Exemplary embodiments of the present invention will hereinafter be described in detail. However, these are only embodiments and the present invention is not limited thereto.
- Non-aqueous rechargeable lithium batteries, according to various embodiments of the present invention, are provided in shapes of a coin, a button, a sheet, or a cylinder. Alternatively, they can be and have other shapes such as flat or prismatic. These rechargeable batteries include a positive electrode, a negative electrode, an electrolyte, a separator, and so on.
- The positive electrode includes an active material of, for example, a Li-based-composite oxide of a transition element such as Ti, Mo, W, Nb, V, Mn, Fe, Cr, Ni, Co, and so on; an organic conductive material of a composite sulfide, vanadium oxide, a conjugated polymer, and so on; and a Chevrel phase compound.
- The negative electrode includes an active material of, for example, a carbon-based active material of graphite, coke, lithium metal, lithium vanadium oxide, lithium transition elements, nitrate, or silicon.
- The positive electrode and negative electrode are obtained by mixing the active material with an additive(s) suitably selected from the group consisting of a conductive agent, a binder, a filler, a dispersing agent, an ion conductive agent, and a pressure enhancer.
- Suitable conductive agents include graphite, carbon black, acetylene black, KETJEN black, carbon fiber, and metal powder. Suitable binders include polytetrafluoro ethylene, polyfluoride vinylidene, and polyethylene.
- In preparing the positive electrode or negative electrode, a mixture of the active material and additives can be added to water or a solvent such as an organic solvent to provide a slurry or a paste. The obtained slurry or paste is coated on an electrode-supported substrate using a doctor blade, and is dried and compressed with a compress roll to provide a positive electrode or a negative electrode.
- Suitable electrode-supported substrates include a foil, a sheet, or a net composed of copper, nickel, stainless steel, aluminum, and so on, or a sheet or net composed of carbon fiber. Alternatively, the positive or negative electrode can be formed by compressing the slurry or paste into a pellet-form without using the electrode-supported substrate.
- Suitable electrolytes include a non-aqueous electrolyte in which lithium salt is dissolved in an organic solvent, a polymer electrolyte, an inorganic solid electrolyte, a polymer electrolyte, and a composite material with an inorganic solid electrolyte.
- Suitable solvents for a non-aqueous electrolyte include cyclic esters such as ethylene carbonate, propylene carbonate, and so on; linear esters such as dimethyl carbonate, diethyl carbonate, methylethyl carbonate, and so on; γ - lactones such as γ -butyl lactone; linear ethers such as 1,2-dimethoxy ethane, 1,2-diethoxy ethane, ethoxymethoxy ethane, and so on; cyclic ethers such as tetrahydrofurans; and nitriles such as acetonitrile and so on.
- Nonlimiting examples of suitable lithium salts for the non-aqueous electrolyte include LiAsF6, LiBF4, LiPF6, LiAlCl4, LiClO4, LiCF3SO3, LiSbF6, LiSCN, LiCI, LiC6H5SO3, LiN(CF3SO2)2, LiC(CF3SO2)3, and LiC4P9SO3.
- The separator body is supported by a composite including an organic compound and an inorganic compound.
- The composite may include any other material as long as it can support the separator body. In one embodiment, the composite is coated on the separator body to form a buffer layer of composite on the surface of the separator body facing the positive electrode and/or the surface facing the negative electrode. In addition, the composite fills the pores of the separator body. In other words, one of the buffer layers of the composite is formed on the surface of the separator body facing the positive electrode and another is formed on the surface facing the negative electrode, and the composite also fills the pores of the separator body.
- In one embodiment, the buffer layer including the composite is formed on the surface of the separator body facing the positive electrode and/or the surface facing the negative electrode. The buffer layer can absorb the volume change created by the expansion and contraction of the electrode during the charge and discharge cycles. Accordingly, the buffer layer can suppress electrode deterioration due to the reactions of the electrode with the separator body.
- Even though the transition element ions included in the positive electrode or the negative electrode are not stable because of the intercalation of lithium ions during the charge and discharge cycles with the positive electrode or negative electrode, the metal ions produced from the inorganic compounds, which are decomposed and eluted in the electrolyte solution, can capture, trap, and stabilize the transition element ions. This stabilization process occurs because the separator body is supported by a composite that has the inorganic compound. Therefore, the separator for a non-aqueous rechargeable lithium battery, according to an embodiment of the present invention, can prevent the deterioration of the electrode due to the electrolyte deposition. One example of an electrolyte deposition includes Li electrodeposition (electrolysis deposition) on the electrode created from a reaction of the positive electrode or negative electrode and the electrolyte solution. The separator can also prevent its own deterioration due to fewer reactions with the positive electrode or negative electrode.
- Some of the reactions will now be described in detail along with specific examples. When the active material of the positive electrode is LiCoO2 and the inorganic compound is Al(OC2H5)3, by way of reference, the transition element ions (Co ions) in the positive electrode material produce unstable quadrivalent cobalt ions (Co4+). At the same time, some of the Al included in the inorganic compound is decomposed and eluted as ionized Al3+ to the electrolyte solution. The Al3+ ions bind with Co2+ ions (formed by reducing the Co4+ ions) in the electrolyte solution to generate Co-AI compounds, which deposit on the surface of the positive electrode and thereby stabilize the surface.
- The separator body may include a porous film composed of a polyolefin such as polypropylene or polyethylene, or a porous material such as a glass filter, a non-woven fabric, and so on. In one embodiment, the separator includes a porous film composed of polyethylene having a melting point ranging from 120 to 140° C. Polyethylene films may be advantageous because they have excellent shutdown characteristics and handling properties and are beneficial in terms of cost.
- According to one embodiment, the separator body has porosity ranging from 40 to 90 volume%. In another embodiment, the separator body has porosity ranging from 50 to 80 volume%.
- When the separator body has porosity ranging from 40 to 90 volume%, the ionic conductivity of the separator increases, so the high discharge characteristic of the non-aqueous rechargeable lithium battery improves. The mechanical strength of the separator also increases and thereby is less prone to damage.
- The separator body may have a thickness of 60 µ m or less. In one embodiment, the thickness of the separator body ranges from 10 to 30 µ m. When the separator body has a thickness of 60 µ m or less, the energy density of the non-aqueous rechargeable lithium battery improves.
- In one embodiment, the organic compound included in the composite has a higher melting point than that of the material of the separator body. That is, the melting point of the organic compound is 180° C or more. In one embodiment, the melting point of the organic compound ranges from 180 to 700° C. In another embodiment, the melting point of the organic compound ranges from 250 to 700° C.
- When the organic compound has a melting point of 180° C or more, the separator structure can be maintained even when the separator body is fused, so short circuits can be prevented.
- Nonlimiting examples of suitable organic compounds may include an aromatic polyamide (hereinafter referred to as "aramid") selected from the group consisting of polypropylene, poly(phenylene terephthalamide), poly(benzamide), poly(4,4'-benzanilideterephthalamide), poly(phenylene-4,4'-biphenylene dicarbonic acid amide), poly(phenylene-2,6-naphthalene dicarbonic acid amide), poly(2-chlorophenylene terephthalamide), and phenylene terephthalamide/2,6-dichlorophenylene terephthalamide copolymers. The optical property of the aramid can be meta or para.
- In various embodiments, the composites including the organic compound and inorganic compound are porous and have a plurality of pores.
- In one embodiment, the buffer layer has porosity ranging from 40 to 90 volume%. In another embodiment, the buffer layer has a porosity ranging from 50 to 90 volume%. In a further embodiment, the porosity ranges from 40 to 60 volume%.
- If the buffer layer has porosity ranging from 40 to 90 volume%, the cushion property improves, so it is possible to absorb the volume change due to the expansion and contraction of the electrode during the charge and discharge cycles. As a result, the electrode is less prone to damage since it has improved mechanical strength.
- In one embodiment, the buffer layer has a thickness (on one side) of 2µm or more. In another embodiment, the buffer layer has a thickness ranging from 2 to 20µm. In a further embodiment, the buffer layer has a thickness ranging from 2 to 10µm.
- When the buffer layer has a thickness of 2 µ m or more, it is possible to absorb the volume change created by to the expansion and contraction of the electrode during the charge and discharge cycles. Because of sufficient reinforcement on the separator body, the separator backbone is maintained to prevent short circuits even after the battery temperature is increased and the separator body is fused. If further safety features for the rechargeable battery are desired, the buffer layer can be made thicker.
- The weight amount of the organic compound of the composite may range from 5 to 50 wt% based on the total weight of the organic compound and inorganic compound. The weight amount of the inorganic compound may range from 50 to 95 wt%. In one embodiment, the amount of the organic compound is 10 to 30 wt% and the amount of the inorganic compound is 70 to 90 wt%. In another embodiment, the amount of the organic compound is 15 to 25 wt% and the amount of the inorganic compound is 75 to 85 wt%.
- When the inorganic compound is included at 50 to 95 wt%, it is possible to sufficiently stabilize the included transition elements because the inorganic compound is sufficiently added and the intensity is improved. Furthermore, when the separator is mounted in the rechargeable battery, it is difficult for it to deteriorate.
- The method of preparing the buffer layer is not limited as described, or as discussed hereafter, but rather is illustrative of how a buffer layer can be prepared.
- When the aramid is used as an organic compound, the aramid is dissolved in a polar organic solvent such as N,N-dimethylformamide, N,N-dimethyl acetamide, N-methyl-2-pyrrolidone, tetramethyl urea, and so on.
- Subsequently, an inorganic compound is dispersed in a polar organic solution to provide a slurry solution. The slurry solution is coated on the surface of the separator body.
- The slurry solution is cured or attached to the surface of the separator body under a certain or set humidity level and at 20° C or more. The aramid dispersed in the inorganic compound precipitates on the surface of the separator body. The separator is immersed in a curing solution including an aqueous solution, polar organic solvent, or an alcoholic solution. The polar organic solvent is then evaporated and removed from the surface of the separator.
- The separator from which the polar organic solvent is removed is dried at a melting point temperature of the separator body to provide a separator formed with a buffer layer on the body surface.
- The present invention is not limited by the following illustrated examples.
- In various examples, the separator body is supported by a buffer layer of composite formed on the surface of the separator body. However, the non-aqueous rechargeable lithium battery according to one embodiment of the present invention can be modified such that the buffer layer including the composite is formed on the surface of the electrode, or it can be placed between the separator body and the negative electrode or the positive electrode by being supported by an electrode-supported substrate independent from the separator body or the electrode.
- As shown in
FIG. 2 , the lithium battery 3 includes anelectrode assembly 4 including a cathode 5, an anode 6, and aseparator 7 positioned between the cathode 5 and anode 6. Theelectrode assembly 4 is housed in abattery case 8, and sealed with acap plate 11 and sealinggasket 12. An electrolyte is then injected into the battery case to complete the battery. - It is to be understood that various embodiments of the present invention may include parts or all of the illustrated examples and modifications thereof. These examples, however, should not in any sense be interpreted as limiting the scope of the present invention.
- 3 parts by weight of N-methyl-2-pyrrolidone solution in which a binder of polyvinylidene fluoride (manufactured by GURYE CHEMICAL CO., LTD. #1100) was dissolved, 95 parts by weight of LiCoO2, and 2 parts by weight of conductive carbon were mixed to provide a positive electrode slurry. The positive electrode slurry was uniformly coated on a 15 µ m-thick Al-foil, and dried to provide a positive electrode. The weight ratio of LiCoO2 : conductive carbon : polyvinylidene fluoride was 95:2:3.
- A mixture of lithium vanadium oxide (LVO) powder and carbon material powder was used as a negative active material. 90 parts by weight of the mixture was mixed with 10 parts by weight of a polyvinylidene fluoride as a binder, and dispersed in N-methyl-2-pyrrolidone to provide a negative electrode slurry. The negative electrode slurry was uniformly coated on a 20 µ m-thick copper foil and dried to provide a negative electrode.
- A polyethylene separator having a buffer layer of a composite, which includes a meta-aramid polymer as an organic compound and other various inorganic compounds shown in Table 1 (for Examples 1 to 9) at a weight ratio of 15:85, coated on each surface of the
separator 4 µ m thick was interposed between the positive electrode and the negative electrode. A 18650-type cylinder rechargeable lithium cell was provided by injecting a non-aqueous electrolyte solution of LiPF6 dissolved in a mixed solvent, which includes ethylene carbonate and diethyl carbonate at a 3:7 weight ratio, at a concentration of 1.50 mol/L. - A polyethylene separator (without a buffer layer) was interposed between a positive electrode and a negative electrode, both of the positive electrode and negative electrode were prepared according to the same procedure as above, and a 18650-type cylinder rechargeable lithium cell was provided using the same above described method.
- Each of non-aqueous rechargeable lithium cells prepared according to Examples 1 to 9 and comparative example was charged at a constant current of 0.5C and constant voltage of 4.3V, and were then discharged to a discharge end voltage of 2.75V at 0.5C, and repeated for 200 cycles. The capacity retention ratio was measured after completing the 200 cycles and the results are provided in Table 1. Examples marked with a "*" are included by way of reference.
Table 1 Inorganic compound Separator body thickness (µm) Thickness of one buffer layer (µm) Capacity retention (%) Example 1 Al2(SO4)3 20 4 92 Example 2 Al2(SO4)3· Al (OC2H5)3 20 4 88 *Example 3 MgCO3 20 4 85 *Example 4 BaCO3 20 4 88 Example 5 Al2O3· AlPO4 20 4 92 *Example 6 MgAl2O4 20 4 85 Example 7 Li2ZrO3 20 4 88 *Example 8 Li2SiO4 20 4 80 *Example 9 Al2O3· Al (OH)3 20 4 81 Comparative Example - 28 - 56 - From the results shown in Table 1, cells having separators with buffer layers of a composite including an organic compound and an inorganic compound formed on both surfaces of the separator body (i.e., Examples 1, 2, 5 and 7) have improved capacity retention after repeating charge and discharge cycles as compared to the cell having only a polyethylene separator (or separator body) interposed between the negative electrode and the positive electrode (i.e., Comparative Example).
- Therefore, according to various embodiments of the present invention, even though the charge and discharge was repeated, it was possible to provide a non-aqueous rechargeable lithium battery having a separator that does not deteriorate or is less prone to deterioration. As a result, it is possible to have batteries having improved overall battery characteristics.
- The separator according to Example 5 and the separator according to the Comparative Example were loaded with a 1.0 kg/cm2 weight. The thickness and compression ratio of each case were measured. The results are shown in Table 2.
Table 2 Thickness without load (µm) Thickness at load (µm) Compression ratio (%) Example 5 28 19 32 Comparative Example 28 26 7 - As shown in Table 2, it is confirmed that the separator of Example 5, which includes a buffer layer on both surfaces, has better compressibility result as compared to that of the separator including only polyethylene according to the Comparative Example. Accordingly, the separator of Example 5 can function as an excellent cushion material when it is disposed between the electrodes.
- Before and after analyzing the capacity retention characteristics, the separator prepared according Comparative Example was analyzed using FT-IR. The results of the Comparative Example are shown in
FIG. 1B . - With respect to the separator prepared according to Example 2, only the buffer layer was analyzed by FT-IR before conducting the capacity retention test; and only the separator body was analyzed by FT-IR after the capacity retention test. The results of Example 2 are shown in
FIG. 1A . - As shown in
FIG. 1B , hydrogen was released, and the peaks of the unsaturated carbonate and oxide were observed at 1200 to 1800 nm in the separator including only polyethylene of the Comparative Example (See the after charge and discharge FT-IR graph line). In contrast, the polyethylene separator body of Example 2, which has buffer layers on both surfaces, was not oxidized even after the capacity retention test was conducted. (SeeFIG. 1A , the after charge and discharge separator body FT-IR graph line, the line is relatively flat in the 1200-1800 nm region.) Accordingly, it is confirmed that oxidation and thereby the deterioration of the separator body was suppressed by the buffer layer(s). - In addition, according to the results of observing the separator body of the Comparative Example and the separator of Example 2 visually, the separator of the Comparative Example was carbonized and the color changed to black, but the separator body of Example 2 for the most part remained the same.
- The present invention can provide a non-aqueous rechargeable lithium battery having improved charge and discharge characteristics as well as safety.
- While the present invention has been described in connection with certain embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the scope of the appended claims.
- The present invention can provide a non-aqueous rechargeable lithium battery having improved charge and discharge characteristics as well as safety.
- While the present invention has been described in connection with certain exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the scope of the appended claims.
Claims (13)
- A separator for a non-aqueous rechargeable lithium battery, comprising:a separator body comprising a material with a first melting point; anda composite supporting the separator body and comprising an organic compound and an inorganic compound, wherein the organic compound has a melting point that is higher than the first melting point, characterised in that the inorganic compound is selected from the group consisting of Al2(SO4)3, Al2(SO4)3·Al(OC2H5)3 Li2MoO3, Al2O3·AlPO4, Li2ZrO3, and combinations thereof.
- A separator according to claim 1, wherein the separator body is supported by a buffer layer of the composite formed on at least one surface of the separator body facing a positive electrode or a negative electrode.
- A separator according to claim 1 or 2, wherein the separator body includes a plurality of pores and the separator body is supported by the composite by having the pores of the separator body filled with the composite.
- A separator according to claim 1, wherein the separator body includes a plurality of pores and the separator body is supported by a buffer layer of the composite on at least one surface of the separator body facing a positive electrode or a negative electrode, wherein the pores of the separator body are filled with the composite.
- A separator according to claim 4, wherein the buffer layer has a thickness ranging from 2 to 20 µ m.
- A separator according to claim 4 or 5, wherein the buffer layer has a porosity ranging from 40 to 90 volume%.
- A separator according to any one of claims 1 to 6, wherein the organic compound has a melting point of 180° C or more.
- A separator according to any one of claims 1 to 7, wherein the organic compound comprises at least one compound selected from the group consisting of polypropylene, aromatic polyamides selected from the group consisting of poly(phenylene terephthalamide), poly(benzamide), poly(4,4'-benzanilideterephthalamide), poly(phenylene-4,4'-biphenyene dicarbonic acid amide), poly(phenylene-2,6-naphthalene dicarbonic acid amide), poly(2-chlorophenyleneterephthalamide), phenylene terephthalamide/2,6-dichlorophenylene terephthalamide copolymers, and combinations thereof.
- A separator according to any one of claims 1 to 8, wherein the composite comprises 5 to 50 wt% of the organic compound and 50 to 95 wt% of the inorganic compound.
- A separator according to any one of claims 1 to 9, wherein the material for the separator body is selected from the group consisting of porous films comprising polypropylene or polyethylene, porous materials comprising glass filters or non-woven fabrics, and combinations thereof.
- A separator according to any one of claims 1 to 10, wherein the material for a separator body is a porous film comprising polyethylene having a melting point ranging from 120 to 140°C.
- A separator according to any one of claims 1 to 11, wherein the separator body has a porosity ranging from 40 to 90 volume%.
- A non-aqueous rechargeable lithium battery comprising:
a separator according to any one of Claims 1 to 12 comprising:a positive electrode facing a first surface of the separator body; anda negative electrode facing a second opposite surface of the separator body.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2007320007A JP5087383B2 (en) | 2007-12-11 | 2007-12-11 | Separator for non-aqueous lithium secondary battery |
JP2007320008A JP5209943B2 (en) | 2007-12-11 | 2007-12-11 | Separator for non-aqueous lithium secondary battery |
Publications (3)
Publication Number | Publication Date |
---|---|
EP2101368A2 EP2101368A2 (en) | 2009-09-16 |
EP2101368A3 EP2101368A3 (en) | 2012-09-05 |
EP2101368B1 true EP2101368B1 (en) | 2018-07-04 |
Family
ID=40467375
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP08253971.9A Active EP2101368B1 (en) | 2007-12-11 | 2008-12-11 | Separator for non-aqueous rechargeable lithium battery |
Country Status (3)
Country | Link |
---|---|
US (1) | US8932746B2 (en) |
EP (1) | EP2101368B1 (en) |
KR (1) | KR100995074B1 (en) |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100947072B1 (en) * | 2008-03-27 | 2010-04-01 | 삼성에스디아이 주식회사 | Electrode Assembly and Secondary Battery having the Same |
JP2010108732A (en) * | 2008-10-30 | 2010-05-13 | Hitachi Ltd | Lithium secondary battery |
KR101084068B1 (en) | 2009-11-25 | 2011-11-16 | 삼성에스디아이 주식회사 | Rechargeable lithium battery |
US8703313B2 (en) | 2010-04-19 | 2014-04-22 | Chun Shig SOHN | Separator for battery |
KR101173866B1 (en) * | 2010-05-28 | 2012-08-14 | 삼성에스디아이 주식회사 | Rechargeable lithium battery |
US8163193B2 (en) * | 2010-08-27 | 2012-04-24 | Tsinghua University | Modifier of lithium ion battery and method for making the same |
CN102479932B (en) * | 2010-11-23 | 2014-04-23 | 清华大学 | Using method of lithium ion battery modifying agent, lithium ion battery diaphragm, and battery |
EP2880701A1 (en) | 2012-07-30 | 2015-06-10 | SABIC Global Technologies B.V. | High temperature melt integrity separator |
WO2019044308A1 (en) | 2017-08-29 | 2019-03-07 | パナソニックIpマネジメント株式会社 | Nonaqueous electrolyte secondary battery |
WO2019246263A1 (en) * | 2018-06-19 | 2019-12-26 | University Of Washington | Battery separator with lithium-ion conductor coating |
US11094998B2 (en) | 2019-06-19 | 2021-08-17 | GM Global Technology Operations LLC | Ceramic-coated separators for lithium-containing electrochemical cells and methods of making the same |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2006068428A1 (en) * | 2004-12-22 | 2006-06-29 | Lg Chem, Ltd. | Organic/inorganic composite microporous membrane and electrochemical device prepared thereby |
WO2007049568A1 (en) * | 2005-10-24 | 2007-05-03 | Tonen Chemical Corporation | Polyolefin multilayer microporous film, method for producing same and battery separator |
EP2169743A1 (en) * | 2007-06-19 | 2010-03-31 | Teijin Limited | Separator for nonaqueous secondary battery, method for producing the same, and nonaqueous secondary battery |
Family Cites Families (28)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3880672A (en) * | 1973-03-23 | 1975-04-29 | Esb Inc | Battery barrier and battery |
US4650730A (en) | 1985-05-16 | 1987-03-17 | W. R. Grace & Co. | Battery separator |
WO1999048163A1 (en) | 1998-03-17 | 1999-09-23 | Mitsubishi Denki Kabushiki Kaisha | Lithium ion battery and method for forming the same |
US6080507A (en) * | 1998-04-13 | 2000-06-27 | Celgard Inc. | Trilayer battery separator |
US6444359B1 (en) | 1998-12-18 | 2002-09-03 | Nec Corporation | Liquid electrolyte solution including a halogenated and aliphatic polyolefin dissolved therein and secondary battery |
DE19916043A1 (en) * | 1999-04-09 | 2000-10-19 | Basf Ag | Composite body suitable for use as a lithium ion battery |
KR100321264B1 (en) | 1999-11-15 | 2002-01-19 | 다니구찌 이찌로오, 기타오카 다카시 | Lithium ion battery and method for forming the same |
US6432586B1 (en) | 2000-04-10 | 2002-08-13 | Celgard Inc. | Separator for a high energy rechargeable lithium battery |
JP2003533862A (en) | 2000-05-19 | 2003-11-11 | コリア インスティテュート オブ サイエンス アンド テクノロジー | Lithium secondary battery including ultrafine fibrous porous polymer separator film and method of manufacturing the same |
TWI315591B (en) * | 2000-06-14 | 2009-10-01 | Sumitomo Chemical Co | Porous film and separator for battery using the same |
KR20030030686A (en) | 2001-10-12 | 2003-04-18 | 삼성에스디아이 주식회사 | Metal cathode for electron tube |
KR100413608B1 (en) * | 2001-10-16 | 2004-01-03 | 주식회사 에너랜드 | Separator for lithium ion secondary batteries, method for producing the same, and lithium ion secondary batteries using the same |
EP1705736B1 (en) | 2003-12-15 | 2015-08-26 | Mitsubishi Chemical Corporation | Nonaqueous electrolyte secondary battery |
JP4929593B2 (en) | 2004-02-10 | 2012-05-09 | 三菱化学株式会社 | Non-aqueous electrolyte secondary battery |
KR100647966B1 (en) | 2004-02-24 | 2006-11-23 | 가부시키가이샤 도모에가와 세이시쇼 | Separator for electronic components and process for producing the same |
US7604895B2 (en) | 2004-03-29 | 2009-10-20 | Lg Chem, Ltd. | Electrochemical cell with two types of separators |
JP4763253B2 (en) | 2004-05-17 | 2011-08-31 | パナソニック株式会社 | Lithium ion secondary battery |
WO2006061936A1 (en) | 2004-12-07 | 2006-06-15 | Matsushita Electric Industrial Co., Ltd. | Separator and nonaqueous electrolyte secondary battery using same |
CA2586062C (en) | 2004-12-08 | 2013-04-02 | Hitachi Maxell, Ltd. | Separator for electrochemical device, and electrochemical device |
JP4743747B2 (en) | 2004-12-08 | 2011-08-10 | 日立マクセル株式会社 | Separator, manufacturing method thereof, and nonaqueous electrolyte battery |
JP5017834B2 (en) | 2005-09-27 | 2012-09-05 | パナソニック株式会社 | Lithium ion secondary battery |
JP5196780B2 (en) | 2005-12-22 | 2013-05-15 | 旭化成イーマテリアルズ株式会社 | Multilayer porous membrane and method for producing the same |
JP2007324073A (en) | 2006-06-05 | 2007-12-13 | Matsushita Electric Ind Co Ltd | Lithium secondary battery, its separator and its manufacturing method |
KR100820162B1 (en) * | 2006-08-07 | 2008-04-10 | 한국과학기술연구원 | Ultrafine fibrous separator with heat resistance and the fabrication method thereof, and secondary battery using the same |
CN101517783B (en) * | 2006-09-25 | 2014-10-08 | 株式会社Lg化学 | Novel separator and electrochemical device comprising the same |
JP2007214137A (en) | 2007-03-12 | 2007-08-23 | Mitsubishi Chemicals Corp | Negative electrode active material for nonaqueous carbon-coated lithium secondary battery |
CN101276895B (en) * | 2007-03-27 | 2013-05-29 | 比亚迪股份有限公司 | Composition for lithium ion secondary battery porous diaphragm layer and lithium ion secondary battery |
CN101779311B (en) | 2007-06-06 | 2013-11-20 | 帝人株式会社 | Polyolefin microporous membrane base for nonaqueous secondary battery separator, method for producing the same, nonaqueous secondary battery separator and nonaqueous secondary battery |
-
2008
- 2008-11-13 KR KR1020080112793A patent/KR100995074B1/en active IP Right Grant
- 2008-12-10 US US12/332,218 patent/US8932746B2/en active Active
- 2008-12-11 EP EP08253971.9A patent/EP2101368B1/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2006068428A1 (en) * | 2004-12-22 | 2006-06-29 | Lg Chem, Ltd. | Organic/inorganic composite microporous membrane and electrochemical device prepared thereby |
WO2007049568A1 (en) * | 2005-10-24 | 2007-05-03 | Tonen Chemical Corporation | Polyolefin multilayer microporous film, method for producing same and battery separator |
EP1942000A1 (en) * | 2005-10-24 | 2008-07-09 | Tonen Chemical Corporation | Polyolefin multilayer microporous film, method for producing same and battery separator |
EP2169743A1 (en) * | 2007-06-19 | 2010-03-31 | Teijin Limited | Separator for nonaqueous secondary battery, method for producing the same, and nonaqueous secondary battery |
Also Published As
Publication number | Publication date |
---|---|
US20090155677A1 (en) | 2009-06-18 |
US8932746B2 (en) | 2015-01-13 |
EP2101368A3 (en) | 2012-09-05 |
KR100995074B1 (en) | 2010-11-18 |
KR20090061571A (en) | 2009-06-16 |
EP2101368A2 (en) | 2009-09-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2101368B1 (en) | Separator for non-aqueous rechargeable lithium battery | |
KR101130471B1 (en) | Lithium secondary battery | |
JP5087383B2 (en) | Separator for non-aqueous lithium secondary battery | |
JP4884774B2 (en) | Method for producing electrode for electrochemical cell | |
KR101430616B1 (en) | Cathode and lithium battery using the same | |
EP2262037B1 (en) | Lithium secondary battery using ionic liquid | |
EP2238643B1 (en) | Pouch-type lithium secondary battery | |
CN111226330A (en) | Positive electrode material for secondary battery and lithium secondary battery comprising same | |
US7659035B2 (en) | Nonaqueous electrolyte secondary battery | |
US20090148771A1 (en) | Cathode and nonaqueous electrolyte battery | |
KR20090020487A (en) | Non-aqueous electrolytic solution secondary battery | |
KR101155914B1 (en) | Positive electrode for lithium ion secondary battery and lithium ion secondary battery including same | |
KR102448303B1 (en) | An organic electrolyte, and secondary battery comprising the same | |
EP2916374B1 (en) | Lithium secondary battery | |
KR102554229B1 (en) | Method for preparing negative electrode for lithium secondary battery | |
EP4160712A1 (en) | Power storage device and electrode or separator used for same | |
US8440351B2 (en) | Positive electrode for lithium ion secondary battery and lithium ion secondary battery including same | |
EP4060761A1 (en) | Cathode for secondary battery, manufacturing method therefor, and lithium secondary battery comprising same | |
JP5209943B2 (en) | Separator for non-aqueous lithium secondary battery | |
US20220393154A1 (en) | Anode active material, method for preparing anode active material, anode comprising same, and lithium secondary battery | |
CN112490489A (en) | Lithium ion secondary battery and method for manufacturing same | |
CN113994512A (en) | Lithium secondary battery and method for manufacturing the same | |
KR20150049893A (en) | A method for manufacturing cathode, a cathode manufactured thereby and a lithium secondary battery including the same | |
CN114424374B (en) | Secondary battery | |
US20070224503A1 (en) | Secondary battery |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 20081217 |
|
AK | Designated contracting states |
Kind code of ref document: A2 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MT NL NO PL PT RO SE SI SK TR |
|
AX | Request for extension of the european patent |
Extension state: AL BA MK RS |
|
PUAL | Search report despatched |
Free format text: ORIGINAL CODE: 0009013 |
|
AK | Designated contracting states |
Kind code of ref document: A3 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MT NL NO PL PT RO SE SI SK TR |
|
AX | Request for extension of the european patent |
Extension state: AL BA MK RS |
|
RIC1 | Information provided on ipc code assigned before grant |
Ipc: H01M 2/18 20060101ALI20120731BHEP Ipc: H01M 2/16 20060101AFI20120731BHEP |
|
AKX | Designation fees paid |
Designated state(s): DE FR GB |
|
17Q | First examination report despatched |
Effective date: 20150528 |
|
RIC1 | Information provided on ipc code assigned before grant |
Ipc: H01M 2/18 20060101ALI20171212BHEP Ipc: H01M 2/16 20060101AFI20171212BHEP Ipc: H01M 10/052 20100101ALN20171212BHEP |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
INTG | Intention to grant announced |
Effective date: 20180119 |
|
INTG | Intention to grant announced |
Effective date: 20180124 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): DE FR GB |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 602008055826 Country of ref document: DE |
|
RIC2 | Information provided on ipc code assigned after grant |
Ipc: H01M 10/052 20100101ALN20171212BHEP Ipc: H01M 2/16 20060101AFI20171212BHEP Ipc: H01M 2/18 20060101ALI20171212BHEP |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 602008055826 Country of ref document: DE |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed |
Effective date: 20190405 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R079 Ref document number: 602008055826 Country of ref document: DE Free format text: PREVIOUS MAIN CLASS: H01M0002160000 Ipc: H01M0050409000 |
|
P01 | Opt-out of the competence of the unified patent court (upc) registered |
Effective date: 20230528 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20231130 Year of fee payment: 16 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20231212 Year of fee payment: 16 Ref country code: DE Payment date: 20231128 Year of fee payment: 16 |